CN107973908A - End group sulfonate type lignin polyether and its preparation method and application - Google Patents
End group sulfonate type lignin polyether and its preparation method and application Download PDFInfo
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- CN107973908A CN107973908A CN201711174083.6A CN201711174083A CN107973908A CN 107973908 A CN107973908 A CN 107973908A CN 201711174083 A CN201711174083 A CN 201711174083A CN 107973908 A CN107973908 A CN 107973908A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/42—Phenols and polyhydroxy ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Abstract
The invention discloses a kind of end group sulfonate type lignin polyether and its preparation method and application, the structure of the polyethers is shown in formula I.In the end group sulfonate type lignin polyether structure of the present invention, the hydrophobic effect of alkali lignin main body macromolecular structure is stronger, and adsorption site is more, can be adsorbed in particle surface multiple spot, plays the role of anchoring absorption；Alkenyl polyethylene glycol long chain provides steric hindrance effect, particle surface is covered with hydrophilic long flexible chain, adsorbed film is had larger steric hindrance effect and elasticity, improves the stably dispersing effect of system；Sulfonic group makes anionic charge on the adsorbed film band of particle surface, adsorbed film is had larger electrostatic repulsion in the outermost layer of adsorbed film, improves the stably dispersing effect of system.The preparation method of the present invention carries out under atmospheric low-temperature, and easily operated control, side reaction is few, the destruction very little to lignin structure；Two-step reaction is only needed, the reaction time is shorter.It is product good water solubility, environment-protecting and non-poisonous.
Description
Technical field
The invention belongs to modified lignin resin field, and in particular to a kind of end group sulfonate type lignin polyether and its preparation side
Method and purposes.The present invention using alkali lignin as raw material, with epoxychloropropane modified alkenyl polyethylene glycol in alkaline aqueous solution into
Lignin polyether is made in row substitution reaction, then double bond progress sulfonation is obtained end group sulfonate type lignin polyether.
Background technology
Lignin is the second largest natural reproducible resource of nature, is the valuable source of human future.At present, can industry
The lignin utilized mostlys come from pulp and paper industry, is broadly divided into water soluble lignosulfonates and difficult water-soluble alkali wood
Quality.
Lignosulfonates are the principal modes that current lignin is industrially applied, due to containing phenylpropyl alcohol alkane in its molecule
The hydrophobic framework and hydrophilic sulfonic group of construction unit composition, therefore molecule has obvious surface-active and physical chemistry spy
Property, has stronger adsorptivity and interfacial activity in liquid-vapor interface and solid-liquid interface, cement, water-coal-slurry, pesticide, ceramics,
The fields such as oil extraction are commonly used for functional aid.Therefore sulfonate type lignin water soluble polymer obtains in the industry
Widely apply, its application study is more mature.
Although the application of sulfonate type lignin water soluble polymer in the industry is very extensive and ripe, usually quilt
It is considered a kind of fine chemical product of " balm " formula, although widely used, efficiency is universal general, it is hard to develop into certain
Efficient, mainstream the Additives Products of a or some industrial circles.Here the reason for, is except water-soluble for sulfonate type lignin
Outside high molecular research will also continue deeper into, the limitation of sulfonate type lignin water soluble polymer self property is also limitation
An important factor for its effectiveness.
The intermediate that patent CN103709409A is obtained using polyethylene glycol and epichlorohydrin reaction is again and alkali lignin
Reaction obtains lignin-base polyoxyethylene ether, since polyethylene glycol both ends all can be with epichlorohydrin reaction, polyethylene glycol
Intermediate containing more in obtained product during lignin reaction again with, there are serious crosslinking phenomena, having complex cross-linked structure
Modified product, the product of single modification is seldom, and the patent is using the directly obtained powder of spray drying, not only expensive,
Impurity can't be removed, there are many drawbacks.
The content of the invention
The present invention primary and foremost purpose be to provide a kind of end group sulfonate type lignin polyether, belong to a kind of the moon/nonionic
The lignin water soluble polymer of type, the product can play absorption peptizaiton, its structural principle and excellent in particle dispersion system
Point is as follows：1. the hydrophobic effect of alkali lignin main body macromolecular structure is stronger, adsorption site is more, can be inhaled in particle surface multiple spot
It is attached, play the role of anchoring absorption；2. alkenyl polyethylene glycol long chain provides steric hindrance effect, particle surface is set to be covered with hydrophily
Long flexible chain, make adsorbed film that there is larger steric hindrance effect and elasticity, improve the stably dispersing effect of system；3. sulfonic acid
Base makes anionic charge on the adsorbed film band of particle surface in the outermost layer of adsorbed film, makes adsorbed film that there is larger electrostatic to denounce
Power, improves the stably dispersing effect of system.
Another object of the present invention is to provide the preparation method of above-mentioned end group sulfonate type lignin polyether.In order to overcome
The serious crosslinking problem occurred in the prior art when lignin and polyethylene glycol intermediate reaction, wood in preparation method of the invention
Without using polyethylene glycol polymeric on quality molecule, but the polyether reactant active with one end, so can be existing to avoid crosslinking
The generation of elephant；Another section of group of polyethers is carbon-carbon double bond, for being grafted sulfonate.
It is still another object of the present invention to provide the purposes of above-mentioned end group sulfonate type lignin polyether.
The purpose of the present invention is achieved through the following technical solutions：
A kind of end group sulfonate type lignin polyether, structure is shown in formula I；
Since lignin molecule amount is very big and molecular structure is complicated, this area is representing related with modified lignin resin
The remaining structure of lignin is usually substituted during structural formula with Lignin, Formulas I also uses this method for expressing, people in the art
Member will readily appreciate that in Formulas I the content that " Lignin " is referred to；
In Formulas I, M+It is preferred that Na+、K+, or NH4 +；
The present invention end group sulfonate type lignin polyether be made of phenylpropyl alcohol alkyl structure unit hydrophobic framework, hydrophily
Nonionic ethylene oxide ether hydrophilic chain and the lignin derivative that is formed with anion of sulfonic acid, be that a kind of new lignin-base is high
Molecule.
The preparation method of above-mentioned end group sulfonate type lignin polyether, comprises the following steps：
(1) 100 parts of alkenyl polyethylene glycol and 4~10 parts of epoxychloropropane are heated to 50~80 DEG C, melting, adds 1~3
Part catalyst, when 50~80 DEG C of reactions 0.5~3 are small, obtains chloro alkenyl polyethylene glycol intermediate；
(2) 50~150 parts of lignin are dissolved in alkaline aqueous solution, are configured to 20~40% solid contents, it is 10 to adjust pH value
~14；Then heat to 50~90 DEG C, the chloro alkenyl polyethylene glycol intermediate of a dropping step (1) middle preparation, after dripping off,
When 50~90 DEG C of insulation reactions 1~3 are small, lignin polyether is obtained；
(3) the pH value of (2) lignin polyether solution that regulating step obtains is 3~7, then adds 10~80 parts of sulfonating agents and exists
When 60~90 DEG C of progress sulfonating reactions 1~3 are small, end group sulfonate type lignin polyether is obtained；
The number is mass fraction；
The obtained reaction product mixed liquor containing end group sulfonate type lignin polyether is poured into a large amount of anhydrous propanones,
End group sulfonate type lignin polyether is set to precipitate, the impurity such as unreacted alkenyl polyethylene glycol, epoxychloropropane is dissolved in
Layer solution, outwells upper solution, removes layer viscous solid and dissolved with ethanol solution, is obtained after evaporating ethanol and moisture
The end group sulfonate type lignin polyether of purification.
The alkenyl polyethylene glycol used in above-mentioned steps only has one end to have alcoholic extract hydroxyl group, and 1mol alkenyls polyethylene glycol is at most only
With 1mol epichlorohydrin reactions, the intermediate of one end modification is obtained；Intermediate during lignin phenol's hydroxyl reaction again with that will not send out
Raw crosslinking, obtains the more single modified product of structure；And by varying lignin dosage, different modified ratios can be obtained
End group sulfonate type lignin polyether.
The step (1) preferred allyl polyglycol of alkenyl polyethylene glycol, methallyl alcohol polyethylene glycol, iso-amylene
One kind in alcohol polyethylene glycol, isobutene alcohol polyethylene glycol or polyethylene glycol acrylate；The alkenyl polyethylene glycol is preferred
Molecular weight is 200~3000；
(2) the lignin is one or more of alkali lignin, solvent lignin or enzymolysis xylogen to step；
The step (1) preferred antimony pentafluoride of catalyst, boron trifluoride ether, aluminium chloride, butter of tin, Antimony pentachloride
Or one or more of tetrabutylammonium bromide；
The step (3) preferred sodium hydrogensulfite of sulfonating agent, sodium pyrosulfite, sodium sulfite, potassium bisulfite, Jiao Ya
One kind in potassium sulfate, potassium sulfite, ammonium bisulfite, ammonium pyrosulfite or ammonium sulfite.
The end group sulfonate type lignin polyether of the present invention, its hydrophobic group is lignin-base aromatic rings, and molecular weight is big, in agriculture
There is strong adsorption capacity on medicine molecule；Hydrophilic group is multiple polyoxyethylene flexibility side chains, and the end of polyoxyethylene branched chain
There is an anion sulfoacid base at end；Therefore there is the sulfonic new hyper-dispersant knot of hydrophobic aromatic ring-polyoxyethylene chain-
Structure；The end group sulfonate type lignin polyether of the present invention can be adsorbed closely on pesticide granules surface, its hydrophilic polyoxy
Ethene flexibility side chain can form thicker steric hindrance adsorption layer on pesticide granules surface, and the sulfonic acid of polyoxyethylene chain end
Base can provide negative electrical charge for adsorption layer outer layer again.
Mechanism and superior function based on more than, end group sulfonate type lignin polyether of the invention may be used as pesticide water
Suspension agent and disperser, the production applied to pesticide suspension concentrate；
The preferred carbendazim of the pesticide.
The present invention is had the following advantages relative to the prior art and effect：
1st, preparation method of the invention carries out under atmospheric low-temperature, easily operated control, due to direct by graft reaction
Alkenyl polyethylene glycol hydrophilic radical is accessed in lignin molecule, side reaction is few, the destruction very little to lignin structure；Only need two
Step reaction, reaction time are shorter.It is product good water solubility, environment-protecting and non-poisonous.
2nd, end group sulfonate type lignin polyether of the invention is respectively provided with good water solubility in different pH value ranges,
And it can be dissolved in methanol, ethanol, chloroform, DMF polar organic solvents.
3rd, end group sulfonate type lignin polyether of the invention enriches the high molecular species of water-soluble lignin and application
Scope, has widened the research category that Liginon Resourceization utilizes technology.
4th, alkenyl polyethylene glycol used in the present invention only has one end to have alcoholic extract hydroxyl group, and 1mol alkenyls polyethylene glycol is at most only
With 1mol epichlorohydrin reactions, the intermediate of one end modification is obtained；Intermediate during lignin phenol's hydroxyl reaction again with that will not send out
Raw crosslinking, obtains the more single modified product of structure.And by varying lignin dosage, different modified ratios can be obtained
End group sulfonate type lignin polyether.
5th, end group sulfonate type lignin polyether of the invention contains lignin macromolecular aromatic rings hydrophobic framework structure, can
Using the hydrophobic group as high molecular surfactant, the essential groups of multi-point-anchoring absorption are may be used as.With wood common at present
Mahogany sulfonate is compared, and sulfonic group is not contained in its lignin host molecule structure, therefore on solid and hydrophobic substance surface
Absorption will not be influenced be subject to hydrophilic sulfonic acid groups, adsorption capacity is stronger；As dispersant, adsorption group is in solid and dredges
Adsorption strength on water goods and materials surface directly affects its performance.The sulfonic group of lignosulfonates is connected directly between lignin
On host molecule, and content is higher, and hydrophily is strong, directly influences the hydrophobicity and adsorption capacity of lignin host molecule, this
And the universal poor reason of lignosulfonates performance.The structure of the present invention successfully solves the problems, such as this.
6th, end group sulfonate type lignin polyether of the invention contains alkenyl polyethylene glycol long chain, is non-ionic flexibility
Hydrophilic long-chain, when the absorption of dispersant host molecule is when on solid and hydrophobic goods and materials surface, alkenyl polyethylene glycol long chain provides empty
Between steric hindrance effect, to the interface adsorbed provide one have resiliency steric hindrance protective layer, prevent particle due to
Brownian movement is collided and flocculated, therefore good dispersion performance is brought to dispersant；With lignosulfonates phase common at present
Than alkenyl polyethylene glycol long chain provides steric hindrance effect, and lignosulfonates do not contain this alkenyl polyethylene glycol long chain.
7th, end group sulfonate type lignin polyether of the invention contains anion sulphur in the end of alkenyl polyethylene glycol long chain
Acidic group, when the absorption of dispersant host molecule is when on solid and hydrophobic goods and materials surface, providing electrostatic to the interface adsorbed arranges
Denounce active force, hinder particle since Brownian movement is collided and flocculate, good dispersion performance is brought to dispersant；With it is current
Common lignosulfonates are compared, its sulfonic group is not directly connected on lignin host molecule, but is gathered by alkenyl
The long chain link of ethylene glycol, therefore the multi-point-anchoring suction-operated of lignin host molecule is not interfered with, and can be at absorption interface
Play the effect of electrostatic repulsion.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of 1 gained end group sulfonate type lignin polyether of embodiment.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 1 gained end group sulfonate type lignin polyether of embodiment.
Embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the pi-allyl alkenyl polyethylene glycol (APEG-750) that 100g molecular weight is 750 is heated to 62 DEG C, melted, dimension
Hold it is temperature-resistant, thereto add 1g antimony pentafluoride catalyst, after stirring evenly, be added dropwise 8g epoxychloropropane, react 1 after dripping off
Hour, that is, obtain pi-allyl alkenyl polyethylene glycol intermediate；
(2) 60g alkali lignins are dissolved in the sodium hydrate aqueous solution of 100ml pH=13, are heated to 70 DEG C, to
Pi-allyl alkenyl polyethylene glycol intermediate is wherein added dropwise, when reaction 2 is small after dripping off, that is, obtains lignin polyether AL-APEG
(750)；
(3) a certain amount of sulfuric acid solution of addition into lignin polyether AL-APEG (750), adjusting pH=6,75 DEG C of temperature, so
15g sodium sulfites are added afterwards and carry out sulfonation, are reacted 3h, that is, are obtained end group sulfonate type lignin polyether LAS (750).
Embodiment 2
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the prenol polyethylene glycol (TPEG-1000) that 100g molecular weight is 1000 is heated to 50 DEG C, melted, dimension
Hold it is temperature-resistant, thereto add 2g boron trifluoride ether catalyst, after stirring evenly, be added dropwise 4g epoxychloropropane, after dripping off
React 0.5 it is small when, that is, obtain prenol polyethylene glycol intermediate；
(2) 50g alkali lignins are dissolved in the sodium hydrate aqueous solution of 75ml pH=14, are heated to 55 DEG C, Xiang Qi
Middle dropwise addition prenol polyethylene glycol intermediate, when reaction 3 is small after dripping off, that is, obtains lignin polyether AL-TPEG (1000)；
(3) a certain amount of sulfuric acid solution is added into lignin polyether AL-APEG (1000), adjusts pH=6.2, temperature 90
DEG C, then add 12g sodium hydrogensulfites and carry out sulfonation, react 2h, that is, obtain end group sulfonate type lignin polyether LTS
(1000)。
Embodiment 3
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the pi-allyl alkenyl polyethylene glycol (APEG-3000) that 100g molecular weight is 3000 is heated to 80 DEG C, melted,
Remain temperature-resistant, add 3g tetrabutylammonium bromide catalyst thereto, after stirring evenly, 6g epoxychloropropane is added dropwise, drips off
When reaction 1.5 is small afterwards, that is, obtain pi-allyl alkenyl polyethylene glycol intermediate；
(2) 100g alkali lignins are dissolved in the sodium hydrate aqueous solution of 400ml pH=10, are heated to 50 DEG C, to
Pi-allyl alkenyl polyethylene glycol intermediate is wherein added dropwise, when reaction 2 is small after dripping off, that is, obtains lignin polyether AL-APEG
(3000)；
(3) a certain amount of sulfuric acid solution is added into lignin polyether AL-APEG (3000), adjusts pH=4.5, temperature 85
DEG C, then add 80g potassium bisulfites and carry out sulfonation, react 1.5h, that is, obtain end group sulfonate type lignin polyether LAS
(3000)。
Embodiment 4
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the methallyl alcohol alkenyl polyethylene glycol (HPEG-1200) that 100g molecular weight is 1200 is heated to 65 DEG C, melted
Melt, remain temperature-resistant, add 1.4g aluminum chloride catalysts thereto, after stirring evenly, 10g epoxychloropropane is added dropwise, drips off
When reaction 3 is small afterwards, that is, obtain methallyl alcohol alkenyl polyethylene glycol intermediate；
(2) 150g alkali lignins are dissolved in the sodium hydrate aqueous solution of 400ml pH=12.5, are heated to 90 DEG C,
Methallyl alcohol alkenyl polyethylene glycol intermediate is added dropwise thereto, when reaction 2.5 is small after dripping off, that is, obtains lignin polyether AL-
HPEG(1200)；
(3) a certain amount of sulfuric acid solution of addition into lignin polyether AL-HPEG (1200), adjusting pH=3,85 DEG C of temperature,
Then 30g potassium sulfites are added and carry out sulfonation, 2h is reacted, that is, obtains end group sulfonate type lignin polyether LHS (1200).
Embodiment 5
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the prenol polyethylene glycol (TPEG-2400) that 100g molecular weight is 2400 is heated to 73 DEG C, melted, dimension
Hold it is temperature-resistant, thereto add 1.8g boron trifluoride ether catalyst, after stirring evenly, be added dropwise 5.5g epoxychloropropane, drop
When reaction 2 is small after complete, that is, obtain prenol polyethylene glycol intermediate；
(2) 80g alkali lignins are dissolved in the sodium hydrate aqueous solution of 200ml pH=12, are heated to 82 DEG C, to
Prenol polyethylene glycol intermediate is wherein added dropwise, when reaction 2 is small after dripping off, that is, obtains lignin polyether AL-TPEG (2400)；
(3) a certain amount of sulfuric acid solution of addition into lignin polyether AL-TPEG (2400), adjusting pH=4,78 DEG C of temperature,
Then 30g sodium hydrogensulfites are added and carry out sulfonation, 1.5h is reacted, that is, obtains end group sulfonate type lignin polyether LTS (2400).
Embodiment 6
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) the methallyl alcohol alkenyl polyethylene glycol (HPEG-200) that 100g molecular weight is 200 is heated to 68 DEG C, melted
Melt, remain temperature-resistant, add 1.5g antimony pentafluoride catalyst thereto, after stirring evenly, 4g epoxychloropropane is added dropwise, drips off
When reaction 2 is small afterwards, that is, obtain methallyl alcohol alkenyl polyethylene glycol intermediate；
(2) 45g alkali lignins are dissolved in the sodium hydrate aqueous solution of 110ml pH=13, are heated to 73 DEG C, to
Methallyl alcohol alkenyl polyethylene glycol intermediate is wherein added dropwise, when reaction 1 is small after dripping off, that is, obtains lignin polyether AL-HPEG
(200)；
(3) a certain amount of sulfuric acid solution of addition into lignin polyether AL-HPEG (200), adjusting pH=7, temperature 60 C, so
10g ammonium bisulfites are added afterwards and carry out sulfonation, are reacted 1h, that is, are obtained end group sulfonate type lignin polyether LHS (200).
Embodiment 7
A kind of preparation method of end group sulfonate type lignin polyether, comprises the following steps：
(1) polyethylene glycol acrylate (MPEG-2000) that 100g molecular weight is 2000 is heated to 75 DEG C, melted, dimension
Hold it is temperature-resistant, thereto add 2.5g aluminum chloride catalysts, after stirring evenly, be added dropwise 7g epoxychloropropane, react 2 after dripping off
Hour, that is, obtain polyethylene glycol acrylate intermediate；
(2) 100g alkali lignins are dissolved in the sodium hydrate aqueous solution of 400ml pH=13.5, are heated to 85 DEG C,
Polyethylene glycol acrylate intermediate is added dropwise thereto, when reaction 3 is small after dripping off, that is, obtains lignin polyether AL-MPEG
(2000)；
(3) a certain amount of sulfuric acid solution of addition into lignin polyether AL-MPEG (2000), adjusting pH=5,80 DEG C of temperature,
Then 45g sodium sulfites are added and carry out sulfonation, 2h is reacted, that is, obtains end group sulfonate type lignin polyether LMS (2000).
Embodiment effect explanation：
1 product of embodiment is purified, the lignin polyether sodium sulfonate mixed liquor obtained after having reacted, poured into a large amount of
In anhydrous propanone, it is precipitated out end group sulfonate type lignin polyether, unreacted alkenyl polyethylene glycol, epoxychloropropane etc.
Impurity is dissolved in upper solution, goes upper solution, removes a layer viscous solid, wooden with end group sulfonate type in ethanol dissolved solid
Plain polyethers, evaporation of solvent are the end group sulfonate type lignin polyether LAS (750) that can be purified.
Infrared spectrum analysis is carried out to end group sulfonate type lignin polyether LAS (750), as shown in Figure 1.
Nuclear magnetic resonance (H is carried out to end group sulfonate type lignin polyether LAS (750)1NMR) analyze, as shown in Figure 2.
Infer the structure of end group sulfonate type lignin polyether produced by the present invention shown in formula I with reference to Fig. 1 and Fig. 2.
LAS (750) is used as dispersant, and preparation becomes 40% carbendazim suspending agent.
Divided as a comparison using sodium lignin sulfonate and triphenylethylene base polyether phosphate triethanolamine salt (601PT) at the same time
Powder.Wherein sodium lignin sulfonate is Russian import, obtained by wood pulp acid polishing；601PT is that current field of pesticide preparation is normal
Phosphoric acid ester dispersant.
When preparing suspending agent, first carbendazim active compound is added to and is sanded in tank, then bonus point powder, wetting agent, defoamer, second
Glycol, aluminium-magnesium silicate, xanthans and water, are made 40% carbendazim suspending agent when sand milling 2 is small.
The formula of three kinds of suspending agents is as shown in table 1.
1 40% carbendazim suspending agent formula of table
Remarks：Each percentage is mass fraction
Heat storage stability experiment is carried out to obtained three groups of suspending agents, the mobility of suspending agent before and after heat is store is probed into, suspends
The performance changes such as rate, particle diameter and syneresis rate.
Heat storage temperature is set as 55 DEG C, a length of 2 weeks when heat is store.Using the viscosity of rheometer test suspending agent, rotating speed is
200r/min.During measure centrifugation syneresis rate, 10mL suspending agents are added into centrifuge tube, are centrifuged under the conditions of rotating speed 3000r/min
30min, separating out the volume of liquid, to account for original suspending agent percentage by volume be syneresis rate.
Performance is as shown in table 2 before and after heat storage.
2 40% carbendazim suspending agent heat storage stability result of the test of table
By LAS (750) it can be seen from the experimental result of table 2 be made suspending agent viscosity and particle diameter be in three samples most
Small value, and good fluidity.After heat storage, each sample viscosity has increased, and the viscosity increase ratio of suspending agent is made in LAS (750)
Example is 21.5%, its numerical value is less than the 23.7% of 601PT samples.Meanwhile the change of size of LAS (750) sample is minimum, suspensibility
Decreasing value is also less than 601PT samples.
Learnt by above-mentioned test result analysis, LAS (750) is used as dispersant and prepares 40% carbendazim suspending agent with preferable
Heat storage stability, viscosity and suspensibility are not much different before and after heat storage, and mobility is preferable, and particle diameter remains unchanged substantially.Use
The suspending agent that sodium lignin sulfonate is prepared as dispersant, thixotropy is strong, and mobility is poor, is not convenient to use.Made using 601PT
The suspending agent prepared for dispersant, overall performance and LAS (750) are similar, but particle diameter is more than LAS (750), and the front and rear change of suspensibility
Change is more than LAS (750), illustrates its size controlling ability and slightly worse than LAS (750) to suspending agent.
In conclusion the end group sulfonate type lignin polyether for preparing of the present invention, using natural reproducible lignin as
Raw material, it is cheap, it is environmentally protective, 40% carbendazim suspending agent is prepared as dispersant, there is good thermodynamic stability, it is comprehensive
Close it is functional, can be as a kind of new and effective lignin-base pesticide dispersing agent.601PT belongs to alkylphenol polyoxyethylene ether
Class dispersant, degraded is slow, has potential eco-toxicity, therefore product of the present invention is expected to substitute the pesticide dispersion of phosphoric acid ester
Agent.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of end group sulfonate type lignin polyether, it is characterised in that structure is shown in formula I；
2. end group sulfonate type lignin polyether according to claim 1, it is characterised in that：In Formulas I, M+For Na+、K+, or
NH4 +。
3. the preparation method of end group sulfonate type lignin polyether described in claim 1, it is characterised in that comprise the following steps：
(1) 100 parts of alkenyl polyethylene glycol and 4~10 parts of epoxychloropropane are heated to 50~80 DEG C, melting, adds 1~3 part and urge
Agent, when 50~80 DEG C of reactions 0.5~3 are small, obtains chloro alkenyl polyethylene glycol intermediate；
(2) 50~150 parts of lignin are dissolved in alkaline aqueous solution, are configured to 20~40% solid contents, adjust pH value for 10~
14；Then heat to 50~90 DEG C, the chloro alkenyl polyethylene glycol intermediate of a dropping step (1) middle preparation, after dripping off,
When 50~90 DEG C of insulation reactions 1~3 are small, lignin polyether is obtained；
(3) the pH value of (2) lignin polyether solution that regulating step obtains is 3~7, then add 10~80 parts of sulfonating agents 60~
When 90 DEG C of progress sulfonating reactions 1~3 are small, end group sulfonate type lignin polyether is obtained；
The number is mass fraction.
4. preparation method according to claim 3, it is characterised in that：Gather obtained containing end group sulfonate type lignin
The reaction product mixed liquor of ether is poured into a large amount of anhydrous propanones, end group sulfonate type lignin polyether is precipitated, unreacted
Alkenyl polyethylene glycol, the impurity such as epoxychloropropane be dissolved in upper solution, outwell upper solution, remove layer viscous solid and use second
Alcoholic solution dissolves, the end group sulfonate type lignin polyether purified after evaporating ethanol and moisture.
5. preparation method according to claim 3, it is characterised in that：(1) the alkenyl polyethylene glycol is pi-allyl to step
Polyethylene glycol, methallyl alcohol polyethylene glycol, prenol polyethylene glycol, isobutene alcohol polyethylene glycol or polyethylene glycol acrylic acid
One kind in ester.
6. preparation method according to claim 3, it is characterised in that：The step (1) alkenyl polyethylene glycol, molecular weight
For 200~3000.
7. preparation method according to claim 3, it is characterised in that：Step (2) the lignin be alkali lignin, it is molten
One or more of agent lignin or enzymolysis xylogen.
8. preparation method according to claim 3, it is characterised in that：(1) the catalyst is antimony pentafluoride, three to step
It is fluorinated one or more of borate ether, aluminium chloride, butter of tin, Antimony pentachloride or tetrabutylammonium bromide.
9. preparation method according to claim 3, it is characterised in that：Step (3) the sulfonating agent be sodium hydrogensulfite,
Sodium pyrosulfite, sodium sulfite, potassium bisulfite, potassium metabisulfite, potassium sulfite, ammonium bisulfite, ammonium pyrosulfite or Asia
One kind in ammonium sulfate.
10. application of the end group sulfonate type lignin polyether in pesticide suspension concentrate is produced described in claim 1 or 2.
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